Essential oils (EOs) from medicinal and aromatic plants (MAPs) are well-known as natural antioxidants. Their addition to extra-virgin olive oil (EVOO) can contribute to reducing fat oxidation. The main aim of this study was to improve both food shelf-life and aromatic flavour of EVOO, adding different EOs of Sicilian accessions of common sage, oregano, rosemary and thyme. The morphological and production characteristics of 40 accessions of MAPs were preliminarily assessed. EOs from the most promising accessions of MAPs were analysed by gas-chromatography and mass spectrometry. Photo-oxidative studies of the EOs were carried out and the determination of the EVOO fatty acids obtained from 4 Italian olive varieties was also made. EO content was on average 1.45% (v/w) for common sage, 3.97% for oregano, 1.42% for rosemary and 5.90% for thyme accessions. The highest average EO yield was found in thyme (172.70 kg ha−1) whilst the lowest (9.30 kg ha−1) in rosemary accessions. The chemical composition of EOs was very different in the four MAPs in the study. No significant change of oleic acid percentage was detected in the mixture of EVOO with EO samples. The results seem to highlight the presence of an antioxidant effect of EOs on EVOO.